Coating filamentous articles with vinylidene chloride compositions



.J. H. REILLY April 8, 1w.

COATING FILAMENTOUS ARTICLES WITH-VINYLIDENE CHLORIDE COMPOSITIONS Filed Aug. I 24, 1938 LL MT 1 g/OAI') a I ATTORNEYS.-

Patented Apr. 8, 1941 COATING FILAMENTGUS ARTICLES WITH VINYLIDENE CHLORIDE COMPOSITIONS John H. Reilly, Midland, Mich, asslgnor to The Dow Chemical Company, Midland, Mich., a cornotation of Michigan Application August 24, 193$,SerlaiNo. 226,489

7 Claims.

This invention relates to a method of and composition for coating wire, cordage, and other continuous filaments, and to the product thereby ob tained.

Among the desirable properties of insulated wire for electrical service are uniformity, flesh-- bility, abrasion resistance, non-flammability, moisture impermeability, high dielectric strength, low power factor, and high softening point of the insulation. Enamel-coated wire is apt to be nonl0 uniform in cross-section and to be brittle, somev enamels tending to chip from the wire, either when flexed or abraded. Some of the synthetic plastics heretofore used for wire coating do not have sufiiciently high sofetening points crare not tough enough for general utility. When many of the synthetic resins are plasticized suficiently to provide flexible coatings, they are too soft for. many types of electrical service and are generally ized by high uniformity, flexibility, abrasion re- 39 sistance, moisture impermeability, non-flammability, high dielectric strength, low power factor, and high softening point. It is a further object to provide a coated wire or similar filamentous poorer dielectrics than the-unplasticized resins.

article, whereof the coating has the aforesaid properties. Another object of the invention isto provide a method whereby a coating having the said desired properties may be applied to wire or other non-thermoplastic continuous filaments, do

such as string, cord, rope, thread, and the liked; I

To the accomplishment of the foregoing and' related ends, the invention, then, consists of the composition, method and product hereinafter fully described and'particularly pointed out in the claims, the annexed drawing set ing forth in detail one mode of carrying out the invention, such disclosed rnode -illustrating, however, but one of various ways in'whichthe principle of the invention may be used.

I have now found that the foregoing objects may be attained by employing,'as the coating composition, a solution or dispersion of polymeric vinylidene chloride in a liquid dispersion medium for the saidpolymer, the said medium boiling above and preferably above cs Suitable examples are orthodichlorobenzene or trichlorobenzene. The said dispersion or solution is obtained by heating the polymer with the chlorinated benzene or other dispersion medium to a temperature above 140 0., and preferably to a temperature of about l50-160 C., and is applied to the wire at or near l50-155 C.

My preferred wire-coating composition comprises the following ingredients, in the stated proportions, by weight:

Vinylidene chloride polymer per cent 25 to 35 Solvent (orthodichlorobenzene 0r trichlorobenzene) "per cent 752to 65 Sodium steal-ate per cent of weight of polymer 0.2 to 2 The polymer which I prefer to employ is that of pure vinylidene chloride, having a softening point of -l90 C. When vinylidene chloride is polymerlzed,.- it contains a minute amount (less than 1 per cent) of an acetone-soluble material which, for the purposes of this invention, should be extracted from the main body of acetone-insoluble polymer in order to increase the stability of the polymer toward heat. The so-purified polymer may be heated continuously'to l50-200 C. without exhibiting darkening or other evidences of decomposition. If the traces of acetone-soluble material are left in the polymer, it may be stabilized against thermal decomposition bythe addition of agents adapted to the purpose, e. g. the dye 011 Red B, Oil Red R (benzene azo-benzene azo-betanaphthol) The desired stabilizing effect is produced by employing about 0.2 per cent of the dye, based on the weight of the polymer in the coating solution. The sodium stearate is used in the coating composition to assist in the dispersion of the polymer in the chlorinated benzene, and to toughen the coating of polymer deposited from the dispersion. The coating composition should not be heated in iron apparatus, since continued contact with hot iron appears to catalyze decomposition of the vinylidene chloride dispersion. Nickel, monel, or ceramic vessels may be used when heating the composition during a coating operation. a

A method of applying a; coating of yinylidene chloride to wire, cordage, or similar continuous filaments, will be described with reference to the annexed drawing.

The single figure of the said annexed drawing is a diagrammatic view of an apparatus wherein may be carried out.

wound on a spool of smaller diameter. Pulley I2 is so positioned with respect to the rest of the apparatus that wire H is drawn vertically from this wheel into the steam-jacketed coating chamber I3, throughorifice Id. The coating pot is is filled with the previously defined coating com- I position lfi 'which is admitted to the pot through an ordinarily closed aperture IS. The temperature of bath i6 is held at 145-l60 C., and preferably near l50-155 C., suitably by heating pot I3 with steam at 55 to 75 pounds gauge pressure. The coating composition It cannot leak through orifice l4 since the composition sets to a semisolid gel at temperatures at or below 1 C.

The wire II is drawn from below vertically through bath it into steam-jacketed heating chamber I8 which is heated to 150-160 C., and optimally to 155 C. with 55-70, and preferably 65 pound steam. Lower temperatures, e. g. those produced by 50 pound gauge steam pressure, cause the coating to blister from the wire, while higher temperatures, producible by 80 pound steam, cause-the coating to flow and drip from the wire. A slow stream of pre-heated air is admitted to the inner tube of heater is through an inlet ll, to sweep from the system solvent vapor escaping from the freshly coated wire. The solvent vapor may be trapped in an absorbcut or by suitable condensing means, and recovered.

The coated, partially dried, and substantially non-tacky wire is drawn from 'heater I8 over a large pulley 22 covered by housing 2!, to which a solvent recovery system may be connected. The diameter of wheel 22 is such that the wire is not sharply bent around a short radius of curvature while passing over the pulley, thus preventing the still porous and partially dried coating from fiattening or sloughing from the wire. Further drying is accomplished in steam-jacketed chamber 23. The substantially dry wire H is conveyed over pulley 26 into a drying oven 21 which is heated with steam at about 140-150 pounds gauge pressure, i. e; at a temperature up to about 185 C.near, but not exceeding, the softening- .prevent the coating from becoming brittle when cold. The heat-treatment is efiected suitably by drawing the wire through the hollow core 2% of an electrically heated, thermally insulated furnace 32. Tne'internal temperature of the furnace is adjusted so that the wire coating, in its brief period in the furnace, is heated to 209 to 220 C. The annealed coating on the wire ii" may be allowed to cool gradually to room temperature, or it may be chilled, e. g. in ice-water, to lower the brittle point of the coating. The finished wire ii" is finally passed over a guide roll 33 and wound on a spool 35 by means of a variable speed drive From'time to time, as needed, the coating composition It in pot l3 may be replenished through the opening H5, or a constant level of the coating able connection with a larger outside supply of the hot composition. I

Motion is imparted to the wire solely by the reel drive 3%, only suflicient tension being'maintained to overcome thefriction of the various pulleys and wire guides. The greater the wire speed, the thicker is the coating, since the cool wire entering the bath l6 through orifice M congeals aportion of the composition, and the more rapidly the wire passes through the bath, the less opportunity is there for the temperature to equalize between the wire and the bath. Alt high coating speeds it is desirable to preheat the wire to coating bath temperature.

The drying oven 28 may, if desired, be replaced bya series of driers similar to Hi and 23, with each successive drier at. a slightly higher temperature, up to about 180 C. The heat treatment accomplished in furnace 29, may also be effected in a heated finishing die or in a bath of hot oil or glycerine at 200-220 C. The arrangement shown is believed to be the better one, since no pressure is applied to the coating, and hence, no distortion occurs during the heat-treating step. Wire coated by the method just described will be found to be perfectly centered in its insulation, and to be uniform in cross-section.

As ,an alternative to the method described wherein the wireis lifted vertically from the coating bath, the wire may be passed downward and vertically out of the coating bath, and an expression to that effect in the claims is intended to include upward ordownward motion of the wire away from the bath.

I have coated single and multiple strand wire according to-the method herein described, using an apparatus similar to that shown in the drawing. The so-obtained coated wire is highly flexible at temperatures down to 0 F. (-18 C.) and the insulation is thoroughly water-proof, nonflammable, highly resistant to abrasion, and has high dielectric strength (greater than 1000-3000 volts per mii, depending on thickness) low power factor, and does not soften enough to how at temperatures below 180 C. The coated wire has a glossy appearance, and for many purposes may be used with no further covering. For some types oi service the wire may be further coated or wrapped with other insulation, e. g. silk, cotton, rubber, and the like, the vinylidene chloride coating providing the desired moisture-proofness and the initial insulation, while added coverings augment the already satisfactory properties of the polymer coat, and dress-up" the wire for decorative purposes, etc, 'or are used to comply with-certain existing statutory requirements laid down before the modern plastics were adapted to this type of service.

The invention has been illustrated with respect to the coating of wire for electrical service. Other continuous filamentous articles-such as rope or string may be coated in an analogous manner, to produce strong, waterproof, long-wearing, chemlcal resistant twine, and the like, which is relatively free from attack by fungus, mold, or

soil bacteria which ordinarily cause rotting and composition may be maintained in pot l3 by suitweakening of cordage. When cordage is so coated it remains flexible enough to be tied readily, but

is somewhat stiffer than the uncoated article. It has been found that the vinylidene chloride coat ing adheres to the cordage, even though bent and twisted in the ordinary uses to which such filaments may be put. Among the places in which such a cord or rope may be put to use with advantage are on board ship, where salt spray rots ropes, or in corrosive atmospheres generally, as, for example, around a chemical factory. Vinylidene chloride-coated ropes will outlast tarred ropes used in making fish nets, and the like, and

are considerably lighter in weight and cleaner to I handle. Similarly, a coating applied in the herein-described manner to a fishing line will give a permanently water-proof, free-running line, especially desirable for casting'or trolling, the said line being sufliciently resistant to abrasion to outlast the ordinary line many times, and havmg, per unit cross-sectional area, far greater tensile strength than the usual lines.

The filaments which may be coated by the present process may be of any material whichis insoluble in the chlorinated benzenes or other dispersion medium employed, and which does not soften, melt or char at coating temperature.

The composition herein described has comprised the polymer of vinylidene chloride. Similar results may be obtained with inter-polymers (co-polymers) of vinylidene chloride with other polymerizable materials. Such co-polymers however, have as a rule considerably lower softening points than the polymer of pure vinylidene chloride alone, hence lower drying and annealing tom.

peratures must be used with the co-polymers,

than those given in the example wherein the poly mer of vinylidene chloride alone is used, The present method is particularly adapted to the coating or" wire or cordage with a composition comprising polymeric vinylidene chloride or those ,of its co-polymers which contain a major proportion of vinylidene chloride and have high softening points (above about 170 C.) and the other desirable properties such as dielectric strength, etc.

Or" the chlorobenzenes disclosed as solvents or dispersing agents, viz. orthodichlorobenzene and trichlorobenzene, I prefer to us trichlorobenzene, partly because of its lower vapor pressure at coating bath temperatures, hence lower solvent oleate as dispersion agents. Because of the com-- bination of desirable results obtained through the use .of sodium stearate in small quantities, i. e. 0.2-2 per cent of the weight of polymer, this compound is preferred.

While the invention. has been illustrated with respect to, and is concerned primarily with, the coating .of substantially continuous filamentous articles, it is to be understood that the general principles involved may likewise be applied to the coating of relatively short individual pieces of any employed and which is non-thermoplastic at coating, drying, and annealing temperatures.

Other modes of applying the principle of my invention may be employed instead of the one explained, change being made as regards the method herein disclosed, provided the step or steps stated byany of the following claims or the equivalent of such stated step or steps be employed.

I therefore pa ticularly point out and distinctly claim as my invention:

1. The method which comprises the steps of moving a wire into and vertically out of a bath at a temperature between about 145 and 160 C., and comprising from 25 to parts by weight of the polymer of vinylidene chloride dispersed in from-75 to 65 parts by weight of trichlorobenzene, moving the freshly coated wire vertically through a zone heated to about 155:5 0., to remove suflicient of the trichlorobenzene from the coated wire so that it may be bent without distortion of the coating, moving the partially dried coated wire through another zone heated to a tempera.- ture near, but not exceeding, the softening point of the polymeric vinylidene chloride whereby remaining traces of trichlorobenzene are substantially completely removed, moving the dried coated wire through a relatively short annealing zone wherein the temperature of the coating is raised to between about 200 and. 220 'C., to obtain a symmetrically coated wire whereof the coating is characterized by uniformity, flexibility, abrasion resistance, moisture-impermeability, nonfiammability, high dielectric strength, low power factor, and softening point above 170 C.

2. The method which comprises the steps of moving a wire into and vertically out of a bath at a temperature between about 145 and 160 0., and comprising from 25 to 35 parts by weight of th polymer of vinylidene chloride dispersed in from 75 to 65 parts by weight of trichlorobenzene, the said bath containing a soap to the extent of abou-t.0.2 to 2 per cent of the weight of the polymer, moving the freshly coated wire vertically through a zone heated to about 155i5 C., to remove sumcient oi the trichlorobenzene from the coated wire so that it may be bent without distortion of the coating, moving the partially dried coated wire through another zone heated to a temperature near, but not exceeding, the softening point of the polymeric vinylidene chloride whereby remaining traces of trichlorobenzene are bility, non-flammability, high dielectric strength,

low power factor, and soi'tening point above 3. The method which comprises thesteps of moving a wire into and vertically out of a bath at a temperature between about and 160 0., and comprising from. 25 to 35 parts by weight of the polymer of vinylidene chloride dispersed in from iii to 65 parts by weight of trichlorobenzene, the said bath containing sodium stearate to the extent of about 0.2 to 2 per cent of the weight of the polymer, and a stabilizer for the said polymer, moving the freshly coated wire vertically through a zone heated to about :5 0., to remove sufiicient oi the trichlorobenzene from the coated wire so that it may be bent without dismaterial not affected by the dispersion medium 7 .rwrtion of sh coating, moving the partially dried ccated wire through another zone heated to a temperature near, but not exceeding, th softening point of the polymeric vinylidene chloride whereby remaining traces of trichlorobenzene are substantially completely removed, moving the dried coated wire through a relatively short anneallng z'one wherein the temperature of the coating is raised to between about 200 and 220 C., to obtain a symmetrically coated wire whereof the coating is characterized by uniformity, flexibility, abrasion resistance, moisture-impermeability, non-flammability, high dielectric strength, low power factor, ,and softening point above 170 C.

fi. The method which comprises moving a filafrom the class consisting of orthodichlorobenzene and trichlorobenzene, moving the freshly coated filamentous article vertically through a zone heated to about 155i5 C., to remove sufiicient of the liquid medium from the coated article so that it may be bent without distortion of the coating, moving the partially dried coated article through another zone heated to a temperature near, but not exceeding, the softening point of" the polymeric material, whereby remaining traces of the. liquid medium are substantially completely removed, moving the dried coated article through a relatively short annealing zone wherein the temperature of the coating is raised to between about 200" and 220 0.. to obtain a symmetrically coated article, whereof the coating is continuous, moisture impermeable, non-inflammable, abrasion resistant, of high tensile strength, and of substantially uniform thickness.

5. The method which comprises the steps of moving a wire into and vertically out of a bath at a, temperature between 145 and 160 0., and comprising from '25 to 35 parts by weight of a polymeric material selected from the group con sisting of the polymer of" vinylidene chloride and those of its co-polymerswhich soften above 170 C., dispersed in from 75 to 65 parts by weight of a liquid medium selected from the class consisting of orthodichlorobenzene and trlc'hlorobenzene, moving the freshly coated wire vertically through a zone heated to about 155:5" (2., to remove suflicient of the liquid medium from the coated wire so that it may be bent without distortion of the coating, moving the partially dried coated wire through another zone heated to a temperature near, but not exceeding, the softening point of the polymeric material whereby remaining traces of the liquid medium are substantially completely removed, moving the dried coated wire .through a relatively short annealing zone wherein the temperature of the coating is raised to between about 200 and 220 0., to obtain a symmetrically coated wire, whereof the coating is continuous, moisture impermeable, non-infla mable, abrasion resistant, of high tensile strength,

and of substantially uniform thickness.

6. The method as claimeddn claim 5, wherein the liquid dispersion medium is orthodichlorobenzene.

7. The method as claimed in claim 5, wherein the liquid dispersion medium is trichlorobenzene.

com: B. may. 

